TW202407061A - Formaldehyde-free aqueous pigment composition and coated articles prepared with the same - Google Patents

Abstract

Disclosed is a formaldehyde-free aqueous pigment composition comprising (A) an aqueous emulsion comprising a hydroxyl group functionalized copolymer, (B) an aqueous dispersion comprising a carboxylic acid group functionalized (co)polymer, (C) pigment and (D) thickener. The aqueous pigment composition can be used for forming delicate printing pattern on the surface of various substrates and has superior performance properties such as washing resistance, bond strength, weathering resistance, yellowing resistance, cracking resistance, delamination resistance, and the like. A coated article having a coating layer formed with the aqueous pigment composition is also disclosed.

Description

Formaldehyde-free water-based pigment composition and coated articles prepared therefrom

The present disclosure relates to a unique formaldehyde-free pigment composition that is printable and water-based, and a coated article, such as clothing, having a colored pattern formed by the use of the pigment composition. Formulations of pigment compositions are specifically designed to achieve excellent performance properties such as wash resistance, color fixation, bonding strength, weather resistance, yellowing resistance, cracking resistance, delamination resistance, and the like.

Pigment compositions are suitable for a variety of applications. For example, it can be used to apply symbols, patterns or characters to the surfaces of various items, such as clothing, tents, packaging materials, containers, vessels, buildings, vehicles, furniture, industrial equipment, household appliances, etc. Pigment compositions with good dispersion stability and uniform fineness can be applied to substrates with a printing press to form delicate and vivid images, patterns or symbols. However, coated (for example, by printing) articles prepared by using this pigment composition face two challenges: the first challenge is how to develop environmentally friendly formulations that do not contain toxic ingredients such as toluene, xylene , benzene, toluene diisocyanate (TDI), heavy metals, volatile organic compounds (VOC), and most importantly formaldehyde; the second challenge is the difficulty in maintaining good mechanical properties, such as washing resistance, color fixation, and bonding strength , weather resistance, yellowing resistance, crack resistance, delamination resistance, and similar properties. Several formaldehyde-free formulations are known in the prior art, but virtually none of them overcome both challenges. Therefore, there has been a long-standing need to develop unique pigment compositions that can be used to produce coated articles that exhibit the performance properties described above even after prolonged exposure to harsh outdoor weather.

After unremitting exploration, we have unexpectedly developed a unique formaldehyde-free pigment composition that can achieve the above goals.

The present disclosure provides a unique formaldehyde-free pigment composition and coated articles prepared using the same.

In a first aspect of the present disclosure, the present disclosure provides a formaldehyde-free aqueous pigment composition comprising: (A) an aqueous emulsion comprising a hydroxyl-functional copolymer derived from polymerization of monomers, with Based on the total weight, these monomers include 0.2 wt% to 15 wt% of at least one hydroxyl-containing ethylenically unsaturated C ₂ -C ₁₂ carboxylic acid monomer, and 70 wt% to 95 wt% of at least one ethylenically unsaturated C ₂ -C ₁₂ monocarboxylic acid monomer, 0.2 wt% to 15 wt% of at least ethylenically unsaturated C ₂ -C ₁₂ dicarboxylic acid monomer; (B) an aqueous dispersion comprising at least one olefin Carboxylic acid group functional (co)polymers which are polymerizations of monomer(s) of unsaturated C ₂ -C ₁₂ carboxylic acid monomers; (C) pigments; and (D) thickeners. According to an embodiment of the first aspect, the water-based pigment composition does not contain formaldehyde or ingredients that can release formaldehyde, such as N-methylol acrylamide (NMA) and N-methylol methacrylamide (NMMA). . According to another embodiment of the first aspect, the water-based pigment composition is a printable water-based composition.

In a second aspect of the present disclosure, the present disclosure provides a coated article, which includes a substrate and a coating layer that at least partially covers one or both sides of the substrate, wherein the coating layer is formed from the formaldehyde-free pigment composition of the present disclosure. . According to an embodiment of the second aspect, the base material may be selected from the group consisting of: woven fabric, non-woven fabric, paper, cardboard, wood, wool, cotton, silk, leather, rubber, plastic film (membrane)/ Film, metal film/sheet, fiberglass fabric, carbon fiber fabric, cement, concrete, and combinations thereof.

As claimed, it is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, all publications, patent applications, patents, and other references mentioned herein are incorporated by reference.

As disclosed herein, "and/or" means "and, or as an alternative". Unless otherwise indicated, all ranges are inclusive of endpoints. The term "carboxylic monomer" includes monomers having carboxylic acid group(s) or any derivative thereof, such as carboxylate anionic groups, esters of carboxylic acids [e.g. (C ₁ - C ₁₆ )alkyl ester], and amide of carboxylic acid. The term "(meth)acrylic" refers to acrylic acid or methacrylic acid, and the term (meth)acrylamide refers to acrylamide or methacrylamide.

Without being limited to any particular theory, the technical breakthrough of the present disclosure mainly lies in the specially designed formula of the pigment composition. In particular, it was found that curable systems prepared by using the following can be used to apply images, patterns, symbols, characters, letters, numbers, etc. on a variety of substrates and exhibit desired performance properties: (A) Aqueous emulsions , which comprises a hydroxyl functional copolymer derived from the polymerization of monomers including from 0.2 wt% to 15 wt%, based on the total weight of the copolymer, of at least one hydroxyl-containing ethylenically unsaturated C ₂ -C ₁₂ carboxylic acid monomers, 70 wt% to 95 wt% of at least one ethylenically unsaturated C ₂ -C ₁₂ monocarboxylic acid monomer, 0.2 wt% to 15 wt% of at least one ethylenically unsaturated C ₂ -C ₁₂ monocarboxylic acid monomer Carboxylic acid monomer; (B) an aqueous dispersion comprising carboxylic acid group functionalization (co-) derived from the polymerization of monomer(s) comprising at least one ethylenically unsaturated _C2 - _C12 carboxylic acid monomer Polymer; (C) Pigment; and (D) Thickener. It has also been found that the types and relative contents of the ingredients used in the above various components can be further modified to achieve further improvements in the performance characteristics of the pigment composition and the coated article. Water-based emulsion (A)

According to embodiments of the present disclosure, aqueous emulsion (A) includes a hydroxyl-functional copolymer derived from the polymerization of monomers, which include 0.2 wt% to 15 wt% of at least one component, based on the total weight of the copolymer. Hydroxy ethylenically unsaturated C ₂ -C ₁₂ carboxylic acid monomer, 70 wt% to 95 wt% of at least one ethylenically unsaturated C ₂ -C ₁₂ monocarboxylic acid monomer, and 0.2 wt% to 15 wt% At least ethylenically unsaturated C ₂ -C ₁₂ dicarboxylic acid monomers.

Hydroxyl-containing ethylenically unsaturated C ₂ -C ₁₂ carboxylic acid monosystem refers to a C ₂ -C ₁₂ carboxylic acid containing at least one ethylenically unsaturated group (for example, vinyl, allyl, etc.) and at least one hydroxyl group Monomer, and examples thereof include: (meth)acrylic acid hydroxy (C ₁ -C ₁₂ ) alkyl ester, crotonic acid hydroxy (C ₁ -C ₁₂ ) alkyl ester, pentenoic acid hydroxy (C ₁ -C ₁₂ ) alkyl ester , 3,3-dimethylpentenoate hydroxy (C ₁ -C ₁₂ ) alkyl ester, hexenoate hydroxy (C ₁ -C ₁₂ ) alkyl ester, heptenoate hydroxy (C ₁ -C ₁₂ ) alkyl ester, Octenoic acid hydroxyl (C ₁ -C ₁₂ ) alkyl ester, nonenoic acid hydroxyl (C ₁ -C ₁₂ ) alkyl ester, decenoic acid hydroxyl (C ₁ -C ₁₂ ) alkyl ester, fumaric acid hydroxyl (C ₁ -C ₁₂ )alkyl ester, di(hydroxy(C ₁ -C ₁₂ )alkyl) fumarate, (hydroxy(C ₁ -C ₁₂ )alkyl) ((C ₁ -C ₁₂ )alkyl ) fumarate, hydroxy (C ₁ -C ₁₂ ) maleate, bis (hydroxy (C ₁ -C ₁₂ ) alkyl) maleate, (hydroxy (C ₁ - ) C ₁₂ )alkyl) ((C ₁ -C ₁₂ )alkyl) maleate, 2-methylmaleic acid hydroxy (C ₁ -C ₁₂ ) alkyl ester, bis(hydroxy(C _{1 )} -C ₁₂ )alkyl) 2-methyl maleate, (hydroxy (C ₁ -C ₁₂ ) alkyl) ((C ₁ -C ₁₂ ) alkyl) 2-methyl maleic acid Ester, hydroxy (C ₁ -C ₁₂ ) alkyl itaconate, di(hydroxy (C ₁ -C ₁₂ ) alkyl) itaconate, (hydroxy (C ₁ -C ₁₂ ) alkyl) ((C ₁ -C ₁₂ ) alkyl) itaconate, 2-methyl-iconate hydroxy (C ₁ -C ₁₂ ) alkyl ester, di(hydroxy (C ₁ -C ₁₂ ) alkyl) 2-methyl- itonate Conate, (hydroxy(C ₁ -C ₁₂ )alkyl) ((C ₁ -C ₁₂ )alkyl) 2-methyl-iconate, glutaconate hydroxy(C ₁ -C ₁₂ )alkyl Ester, bis(hydroxy(C ₁ -C ₁₂ )alkyl)glutenedioate, (hydroxy(C ₁ -C ₁₂ )alkyl)((C ₁ -C ₁₂ )alkyl)glutenedioate, Muconate hydroxy (C ₁ -C ₁₂ ) alkyl ester, di(hydroxy (C ₁ -C ₁₂ ) alkyl) muconate, (hydroxy (C ₁ -C ₁₂ ) alkyl) ((C ₁ -C ₁₂ )Alkyl) muconate, or combinations thereof. As used herein, the term "hydroxyl ₍ C ₁ -C ₁₂ )alkyl" refers to a ( _{C 1 -C 12} )alkyl having one hydrogen atom attached to any carbon atom The groups have been substituted with hydroxyl groups. In particular, the hydroxyl-containing ethylenically unsaturated C ₂ -C ₁₂ carboxylic acid monomer may be selected from the group consisting of: hydroxymethyl methacrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate ester, hydroxypropyl methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate, hydroxybutyl acrylate, hydroxyethyl crotonate, and combinations thereof.

According to embodiments of the present disclosure, the content of the hydroxyl-containing ethylenically unsaturated C ₂ -C ₁₂ carboxylic acid monomer may be 0.2 wt% to 15 wt%, such as 0.5-12 wt% based on the total weight of the hydroxyl functional copolymer. wt%, or 0.8-10 wt%, or 1-8 wt%, or 1.2-6 wt%, or 1.4-5 wt%, or 1.5-3 wt%, or 1.6-2.8 wt%, or 2-2.2 wt %, or within a range of values obtained by combining any two of the following endpoint values: 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt %, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%, 3.5 wt%, 3.8 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt %, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt%, 15 wt%.

Ethylenically unsaturated C ₂ -C ₁₂ monocarboxylic acid monosystem refers to a C ₂ -C ₁₂ monocarboxylic acid that contains an ethylenically unsaturated group (for example, vinyl, allyl, etc.) and a carboxyl group and does not have a hydroxyl group Acid monomer, and examples thereof may be selected from the group consisting of: (meth)acrylic acid, crotonic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, and Its salt, anhydride, or (C ₁ -C ₁₂ ) alkyl ester. In particular, the ethylenically unsaturated C ₂ -C ₁₂ monocarboxylic acid monomer may be selected from the group consisting of: acrylic acid, methacrylic acid, crotonic acid, methyl methacrylate, methyl acrylate, ethyl methacrylate , ethyl acrylate, propyl methacrylate, propyl acrylate, butyl methacrylate, butyl acrylate, methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate, and combinations thereof. According to certain embodiments of the present disclosure, ethylenically unsaturated C ₂ -C ₁₂ monocarboxylic acid monomers include mixtures of (meth)acrylic acid and (C ₁ -C ₄ )alkyl (meth)acrylate, such as acrylic acid and acrylic acid Mixture of butyl esters.

According to embodiments of the present disclosure, the content of the ethylenically unsaturated C ₂ -C ₁₂ monocarboxylic acid monomer may be 70 wt% to 95 wt%, such as 74-92 wt% based on the total weight of the hydroxyl functional copolymer. , or 78-90 wt%, or 80-89 wt%, or 84-88 wt%, or 85-88 wt%, or 86-87.5 wt%, or 87-87.5 wt%, or in combination with the following endpoints Within the numerical range obtained by any two values: 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt% , 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%. According to another embodiment of the present disclosure, the ethylenically unsaturated C ₂ -C ₁₂ monocarboxylic acid monomer may include a mixture of (meth)acrylic acid and (C ₁ -C ₄ ) alkyl (meth)acrylate, wherein The content of (meth)acrylic acid may be 1 to 20 wt% based on the total weight of the hydroxyl functional copolymer, such as 1.2-16 wt%, or 1.5-12 wt%, or 2-10 wt%, or 2.2-8 wt%, or 2.4-5 wt%, or 2.7-3 wt%, or within a numerical range obtained by combining any two of the following endpoint values: 1 wt%, 1.2 wt%, 1.4 wt%, 1.5 wt% , 1.8 wt%, 2 wt%, 2.2 wt%, 2.4 wt%, 2.5 wt%, 2.7 wt%, 2.8 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt% , 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt%, 15 wt%, 15.5 wt%, 16 wt%, 16.5 wt%, 17 wt%, 17.5 wt%, 18 wt%, 18.5 wt%, 19 wt%, 19.5 wt%, 20 wt%; and based on the total weight of the hydroxyl functional copolymer, the content of (meth)acrylic acid (C ₁ -C ₄ ) alkyl ester can be 60 to 90 wt%, such as 65-90 wt%, or 70-89 wt%, or 72-88 wt%, or 75-87 wt%, or 78-86 wt%, or 80-85 wt%, or 82- 84.5 wt%, or within the numerical range obtained by combining any two of the following endpoint values: 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt %, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%. According to embodiments of the present disclosure, the ethylenically unsaturated C ₂ -C ₁₂ monocarboxylic acid monomer includes 0.5-5 wt%, such as 1-3 wt% acrylic acid and 75- 86 wt%, for example a mixture of 82-86 wt% butyl acrylate.

Ethylenically unsaturated C ₂ -C ₁₂ dicarboxylic acid monomer refers to a C ₂ -C ₁₂ carboxylic acid monomer that contains at least one ethylenically unsaturated group and two carboxyl groups and does not have a hydroxyl group, and examples thereof can be selected from A group consisting of: fumaric acid, maleic acid, 2-methylmaleic acid, itaconic acid, 2-methyliconic acid, glutaconic acid, muconic acid, and Its salt, anhydride or ester. In particular, the ethylenically unsaturated C ₂ -C ₁₂ dicarboxylic acid monomer may be selected from the group consisting of fumaric acid, maleic acid, itaconic acid, fumaric acid (C ₁ -C ₆ ) alkyl ester, di((C ₁ -C ₆ ) alkyl) fumarate, maleic acid (C ₁ -C ₆ ) alkyl ester, di((C ₁ -C ₆ ) Alkyl)maleate, (C ₁ -C ₆ )alkyl itaconate, di((C ₁ -C ₆ )alkyl itaconate), and combinations thereof.

According to embodiments of the present disclosure, the content of the ethylenically unsaturated C ₂ -C ₁₂ dicarboxylic acid monomer may be 0.2 wt% to 15 wt%, such as 0.3-12 wt% based on the total weight of the hydroxyl functional copolymer. , or 0.4-10 wt%, or 0.5-8 wt%, or 0.8-7 wt%, or 1-6 wt%, or 1.2-5 wt%, or 1.3-4 wt%, or 1.4-3 wt%, or 1.5-2.5 wt%, or 1.6-2 wt%, or within a numerical range obtained by combining any two of the following endpoint values: 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt %, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt %, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%. According to specific embodiments, the ethylenically unsaturated C ₂ -C ₁₂ dicarboxylic acid monomer contains 0.5-2 wt% itaconic acid.

According to embodiments of the present disclosure, the monomers used to prepare the hydroxyl functional copolymer further include at least one additional comonomer selected from the group consisting of: styrenic monomers, ( Meth)acrylamide, butadiene, isoprene, vinyl acetate, (meth)acrylonitrile, and combinations thereof; wherein styrenic monomers include styrene and any derivatives thereof, such as α-methane styrene (AMS), benzyl acrylate, 2-phenoxyethyl acrylate, butyl styrene, methyl styrene, methoxy styrene, hydroxystyrene, or any combination thereof. The content of additional comonomers may be 0 to 20 wt%, such as 0 wt%, or 0.5-18 wt%, or 1-17 wt%, or 2-16 wt%, based on the total weight of the hydroxyl functional copolymer. , or 4-15 wt%, or 5-12 wt%, or 6-10 wt%, or 8-9 wt%; or within a range of values obtained by combining any two of the following endpoint values: 0 wt% , 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%. According to specific embodiments, the additional comonomers comprise 7-10 wt% styrene.

According to another embodiment of the present disclosure, the aqueous emulsion (A) may be a two-stage emulsion having the following: (i) a first-stage component, which includes the above-mentioned hydroxyl functional copolymer; and (ii) A second stage component comprising a (co)polymer derived from the polymerization of monomer(s) including one or more ethylenically unsaturated monomers. The ratio between the solid weight of the first stage component and the solid weight of the second stage component may be 20:1 to 1:1, such as 15:1 to 2:1, or 12:1 to 5:1, or 10:1 to 6:1, or 9:1 to 8:1.

According to another embodiment of the present disclosure, the ethylenically unsaturated monomer of the second stage component may be selected from the group consisting of: (meth)acrylic acid, crotonic acid, pentenoic acid, hexenoic acid, heptenoic acid , octenoic acid, nonenoic acid, decenoic acid, fumaric acid, maleic acid, 2-methylmaleic acid, itaconic acid, and their salts, anhydrides, (C ₁ -C ₁₂ ) Alkyl ester, or hydroxy (C ₁ -C ₁₂ ) alkyl ester; hydroxyl functional ethylenically unsaturated C ₂ -C ₁₆ carboxylic acid; styrenic monomer; (meth)acrylamide; diene ; (C ₁ -C ₁₀ ) vinyl carboxylate; (meth) acrylonitrile; and combinations thereof; wherein styrenic monomers include styrene and any derivatives thereof, such as α-methylstyrene (AMS), Benzyl acrylate, 2-phenoxyethyl acrylate, butylstyrene, methylstyrene, methoxystyrene, hydroxystyrene, or any combination thereof. In particular, the ethylenically unsaturated monomer of the second stage component may be selected from the group consisting of: methacrylic acid, acrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, and others. (C ₁ -C ₆ )alkyl, its hydroxyl group (C ₁ -C ₆ )alkyl; styrene, (meth)acrylamide, butadiene, isoprene, vinyl acetate, (methyl) Acrylonitrile, and combinations thereof. According to specific embodiments, the ethylenically unsaturated monomer of the second stage component may be a mixture of styrene and acrylic acid, such as a mixture of 50-90 wt% styrene and 10-50 wt% acrylic acid.

As used herein, the term "aqueous emulsion" refers to a dispersion of water-insoluble polymers that can be prepared by conventional polymerization techniques, such as by emulsion polymerization. The aqueous emulsion (A) of the present disclosure may be prepared by emulsion polymerization of the above-described monomer/comonomer(s) in a suitable solvent such as water, with one or more additives or processing aids, such as surfactants , initiators, catalysts, cross-linking agents, chain transfer agents, buffers, pH adjusters, or combinations thereof are optionally used in emulsion polymerization reactions as needed. According to the embodiment in which the aqueous emulsion is a two-stage emulsion, the two-stage emulsion can be prepared by sequentially adding the raw materials of each stage into an emulsion polymerization vessel. For example, a two-stage emulsion can be prepared by adding the monomers/comonomers of the first stage first, and then adding the monomers/comonomers of the second stage when the polymerization of the first stage has been completed or substantially completed. Without being bound to any particular theory, two-stage emulsion polymerization can produce an aqueous emulsion containing polymer particles with certain morphologies, such as a mixed-phase structure (in which a first-stage polymer is blended with a second-stage polymer) or a core-shell structure. -shell) structure (in which a first-stage polymer core is partially or completely surrounded by a second-stage polymer shell). Without being bound to any particular theory, aqueous pigment compositions prepared using such two-stage aqueous emulsions may have improved performance properties (such as color fixation, wash resistance, etc.) relative to aqueous pigment compositions prepared using one-stage aqueous emulsions. Sexuality, etc.) exhibit additional enhancements.

Emulsion polymerization can be performed at temperatures from ambient to 120°C, such as 40°C to 100°C, or 50°C to 90°C, or 60°C to 84°C, in air or under the protection of an inert atmosphere (e.g., nitrogen or argon) proceed below.

Conventional surfactants include anionic emulsifiers, nonionic emulsifiers, or combinations thereof. Typical anionic emulsifiers include, but are not limited to, alkali metal alkyl sulfates or ammonium alkyl sulfates, alkali metal alkyl ether sulfates or ammonium alkyl ether sulfates, alkali metal alkylaryl ether sulfates or alkylaryl ether ammonium sulfates, alkali Metal alkyl sulfonates or ammonium alkyl sulfonates, salts of fatty acids, esters of sulfosuccinates, alkyl diphenyl ether disulfonates, and salts or free acids of complex organic phosphates. Typical nonionic emulsifiers include, but are not limited to, polyethers such as poly(ethylene oxide) or poly(propylene oxide). According to certain embodiments of the present disclosure, the surfactant includes a dodecylbenzene sulfonate, such as sodium dodecylbenzene sulfonate. Based on the total weight of the aqueous emulsion, the content of the surfactant may be 0.1 wt% to 5 wt%, such as 0.5-4.5 wt%, or 1-4 wt%, or 1.5-3 wt%, or 2-2.5 wt%. , or within a range of values obtained by combining any two of the following endpoint values: 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt% , 0.9 wt%, 1 wt%, 1.2 wt%, 1.3 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.2 wt%, 2.3 wt%, 2.5 wt%, 2.6 wt%, 2.8 wt%, 3 wt%, 3.1 wt%, 3.2 wt%, 3.5 wt%, 3.6 wt%, 3.8 wt%, 4 wt%, 4.1 wt%, 4.2 wt%, 4.5 wt% , 4.8 wt%, 5 wt%.

The initiator may include an azo initiator, a peroxide initiator, and a redox initiator, and specific examples of the initiator include azobisisobutyronitrile (ABIN), azobisisoheptanitrile ( ABVN), ammonium persulfate (APS), sodium persulfate (SPS), benzyl peroxide (BPO), diisopropyl peroxydicarbonate (IPP), dilauryl peroxide (LPO), hydroperoxide Tertiary butyl oxide (t-BHP), and formed by combining any of the peroxides indicated above with reducing agents such as erythorbic acid (IAA), Fe( _SO4 ) ₂ , etc. Redox initiator system. According to specific embodiments of the present disclosure, the starter includes APS, t-BHP/IAA, or t-BHP/IAA/Fe(SO ₄ ) ₂ . Based on the total weight of the aqueous emulsion, the content of the starter may be 0.1 wt% to 9 wt%, such as 0.5-8 wt%, or 1-6 wt%, or 2-5 wt%, or 3-4 wt%. , or within a range of values obtained by combining any two of the following endpoint values: 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt% , 0.9 wt%, 1 wt%, 1.2 wt%, 1.3 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.2 wt%, 2.3 wt%, 2.5 wt%, 2.6 wt%, 2.8 wt%, 3 wt%, 3.1 wt%, 3.2 wt%, 3.5 wt%, 3.6 wt%, 3.8 wt%, 4 wt%, 4.1 wt%, 4.2 wt%, 4.5 wt% , 4.8 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 6.8 wt%, 7 wt%, 7.2 wt%, 7.5 wt%, 7.8 wt%, 8 wt%, 8.2 wt%, 8.5 wt%, 9 wt%.

According to embodiments of the present disclosure, the water content of the aqueous emulsion (A) is 40 wt% to 95 wt%, such as 45-90 wt%, or 48-80 wt%, or 50-70 wt%, or 55-60 wt%, or within a range obtained by combining any two of the following endpoint values: 40 wt%, 42 wt%, 45 wt%, 48 wt%, 50 wt% , 52 wt%, 55 wt%, 58 wt%, 60 wt%, 62 wt%, 65 wt%, 68 wt%, 70 wt%, 72 wt%, 75 wt%, 78 wt%, 80 wt%, 82 wt%, 85 wt%, 88 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%. Tap water, distilled water, redistilled water, or ionized water may be selected based on the specific application or industry standard of the pigment composition of the present disclosure.

Based on the total weight of the aqueous pigment composition, the relative content of the aqueous emulsion (A) may be 2 wt% to 18 wt%, or 4-16 wt%, or 6-14 wt%, or 8-12 wt%, or 9-10 wt%, or within the range obtained by combining any two of the following endpoint values: 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt %, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 8.8 wt%, 8.9 wt%, 9 wt%, 9.2 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt %. Aqueous dispersion (B)

According to embodiments of the present disclosure, the ethylenically unsaturated C ₂ -C ₁₂ carboxylic acid monomer of the aqueous dispersion (B) may be selected from the group consisting of: (meth)acrylic acid, crotonic acid, pentenoic acid, hexane Enoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, fumaric acid, maleic acid, 2-methylmaleic acid, itaconic acid, 2-methylethanoic acid Conic acid, glutaconic acid, muconic acid, and salts, anhydrides, or (C ₁ -C ₁₂ ) alkyl esters thereof. In particular, the ethylenically unsaturated C ₂ -C ₁₂ carboxylic acid monomer of the aqueous dispersion (B) may be selected from the group consisting of: methacrylic acid, acrylic acid, crotonic acid, fumaric acid, maleic acid Diacid, itaconic acid, methacrylic acid (C ₁ -C ₆ ) alkyl ester, acrylic acid (C ₁ -C ₆ ) alkyl ester, crotonic acid (C ₁ -C ₆ ) alkyl ester, fumaric acid (C ₁ -C ₆ )alkyl ester, di((C ₁ -C ₆ )alkyl) fumarate, maleic acid (C ₁ -C ₆ )alkyl ester, di((C ₁ -C ₆ )alkyl) )alkyl)maleate, (C ₁ -C ₆ )alkyl itaconate, di((C ₁ -C ₆ )alkyl) itaconate, and combinations thereof. According to an exemplary embodiment, the aqueous dispersion (B) may comprise an acrylic (co)polymer, such as a copolymer of methacrylic acid and acrylic acid, especially 50-85 wt% acrylic acid and 15-50 wt% based on the total weight of the copolymer. Copolymer of wt% methacrylic acid.

Aqueous dispersion (B) may be produced by common techniques such as solution polymerization, emulsion polymerization, or dispersion polymerization, optionally in the presence of any common additives or processing aids, such as surfactants, initiators, chain transfer agents, Coupling agents, cross-linking agents, chain extenders, etc.

According to embodiments of the present disclosure, the solid content of the aqueous dispersion (B) may be 25 wt% to 55 wt%, such as 28-50 wt%, or 30-55 wt, based on the total weight of the aqueous dispersion (B). %, or 32-50 wt%, or 35-40 wt%, or within a numerical range obtained by combining any two of the following endpoint values: 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt %, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%.

Based on the total weight of the aqueous pigment composition, the relative content of the aqueous dispersion (B) may be 0.05 wt% to 5 wt%, or 0.1-4 wt%, or 0.2-3 wt%, or 0.3-2 wt%, or 0.4-1 wt%, or within the numerical range obtained by combining any two of the following endpoint values: 0.05 wt%, 0.06 wt%, 0.08 wt%, 0.1 wt%, 0.12 wt%, 0.15 wt%, 0.18 wt%, 0.2 wt%, 0.22 wt%, 0.25 wt%, 0.28 wt%, 0.3 wt%, 0.32 wt%, 0.35 wt%, 0.38 wt%, 0.4 wt%, 0.42 wt%, 0.45 wt%, 0.48 wt% ,0.5 wt%, 0.52 wt%, 0.55 wt%, 0.58 wt%, 0.6 wt%, 0.65 wt%, 0.7 wt%, 0.75 wt%, 0.8 wt%, 0.85 wt%, 0.9 wt%, 0.95 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%. additives

Any conventional pigment may be selected to impart the desired color to the aqueous pigment composition of the present disclosure. Pigments may be transparent, translucent, or opaque, and exemplary pigments include azo pigments, phthalocyanine pigments, allionquinone pigments, indigo pigments, quinacridone pigments, dioxins pigments, arylmethane pigments, or combinations thereof. According to embodiments of the present disclosure, the pigment may be in the form of a dispersion, such as an aqueous dispersion, having about 20 wt% to 60 wt%, such as 25 wt% to 55 wt%, or 30-50 wt%, or 35- 45 wt%, or 40-45 wt% solid content.

According to another embodiment, the aqueous pigment composition of the present disclosure includes 0.5 wt% to 10 wt% of pigments, such as 1-9 wt%, or 2-8 wt%, or 3 based on the total weight of the aqueous pigment composition. -7 wt%, or 4-6 wt%, or 5-5.5 wt%, or within the numerical range obtained by combining any two of the following endpoint values: 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.2 wt%, 1.4 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%, 3.2 wt% , 3.5 wt%, 3.8 wt%, 4 wt%, 4.2 wt%, 4.5 wt%, 4.8 wt%, 5 wt%, 5.2 wt%, 5.5 wt%, 5.8 wt%, 6 wt%, 6.2 wt%, 6.5 wt%, 6.8 wt%, 7 wt%, 7.2 wt%, 7.5 wt%, 7.8 wt%, 8 wt%, 8.2 wt%, 8.5 wt%, 8.8 wt%, 9 wt%, 9.2 wt%, 9.5 wt% , 9.8 wt%, 10 wt%.

Thickeners include any compound commonly used to increase the viscosity and consistency of the aqueous pigment compositions of the present disclosure, and exemplary thickeners may include polypropylene thickeners, polyurethane thickeners, cellulose thickeners, Thickeners (such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose), polyether thickeners (such as polyethylene oxide, AES), polyester thickeners ( For example, PEG-150 distearate), aliphatic acid thickeners (such as lauric acid, linoleic acid, linolenic acid, myristic acid, stearic acid), aliphatic alcohol thickeners (such as lauryl alcohol , myristyl alcohol, decanol, hexanol, octanol, cetyl alcohol, stearyl alcohol, behenyl alcohol), inorganic salt thickeners (such as monoethanolamine chloride, diethanolamine chloride, sodium sulfate, sodium phosphate , disodium phosphate, and pentasodium triphosphate), alkanolamide thickeners (such as coco diethanolamide), amine oxide thickeners, natural gum thickeners (such as starch, gum arabic, fruit Glue, agar, gelatin, algin, carrageenan, dextrin, gelatin, soluble starch, polysaccharide), and combinations thereof. According to a specific embodiment, the aqueous pigment composition of the present disclosure includes 0.1 wt% to 15 wt% thickener, such as 0.2-12 wt%, or 0.5-10 wt%, or 0.8-8 wt%, or 1-5 wt%, or 1.5-2 wt%, or within a numerical range obtained by combining any two of the following endpoint values: 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt %, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%, 3.2 wt%, 3.5 wt%, 3.8 wt%, 4 wt%, 4.2 wt%, 4.5 wt%, 4.8 wt%, 5 wt%, 5.2 wt%, 5.5 wt%, 5.8 wt%, 6 wt%, 6.2 wt%, 6.5 wt%, 6.8 wt%, 7 wt%, 7.5 wt %, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt%, 15 wt%.

The water-based pigment composition may further contain conventional additives, such as fillers, synergists, anti-migration auxiliaries, curing agents, coalescents, biocides, plasticizers, organosilanes, Defoaming agents, corrosion inhibitors, waxes, or antioxidants.

According to a specific embodiment, the water-based pigment composition is formaldehyde-free, which means that the composition does not substantially contain formaldehyde and does not release a large amount of formaldehyde due to drying and/or curing. In order to minimize the formaldehyde content of the aqueous pigment composition, the preparation of the aqueous pigment composition of the present invention, especially the polymerization for the preparation of aqueous emulsions and aqueous dispersions, particularly selects formaldehyde-free reagents, such as co-monomers, initiators, reducing agents, etc. agents, chain transfer agents, surfactants, cross-linking agents, and the like, which themselves do not contain formaldehyde, do not generate formaldehyde during the polymerization process and do not generate or emit formaldehyde during the manufacture of coated/printed substrates. According to embodiments, the raw materials used to prepare the aqueous pigment composition do not intentionally contain any substances that generate formaldehyde during manufacturing, packaging, transportation, storage, application, and long-term weathering. For example, the water-based pigment composition of the present disclosure does not contain N-methylol acrylamide (NMA) and N-methylol methacrylamide (NMMA), which are often referred to as formaldehyde-emitting compounds. combination agent.

The aqueous pigment composition of the present disclosure can be prepared by bending the aqueous emulsion (A), aqueous dispersion (B), pigment, thickener, water, and any additional additives (if present) under stirring. Application

Also disclosed is a method of producing coated articles using an aqueous pigment composition and coated articles prepared by using the same. The water-based pigment composition of the present disclosure can be used in various applications, such as clothing, tents, packaging materials, containers, utensils, buildings, vehicles, furniture, industrial equipment, household appliances, etc. The water-based pigment composition can be produced by any appropriate technique, such as gravure coating, roller coating, knife coating, cast coating, spray coating, dip coating, die coating, blade coating, printing, etc. Applied to one or more substrate surfaces to form a coating, such as a pigment coating, that partially or completely covers the substrate surface. Depending on the specific application, the substrate may be made of a material selected from the group consisting of: woven, nonwoven, paper, cardboard, wood, wool, cotton, silk, leather, rubber, plastic film/film, metal film /Sheet, fiberglass fabric, carbon fiber fabric, cement, concrete, and combinations thereof. The coating can be a colored layer covering the entire surface of the substrate. Alternatively, the coating may be applied to portions of the substrate surface (in continuous or discrete form) to form images, patterns, letters, characters, symbols, or random shapes.

Figure 1 shows a schematic view of an article, in particular clothing, having letters formed by printing an aqueous pigment composition onto selected surface portions, and Figure 2 shows a cross-sectional view of the garment. Letters formed from water-based pigment compositions bond firmly to the substrate and do not exhibit substantial peeling or color change even after prolonged use and repeated laundering cycles. Example

Some embodiments of the invention will now be described in the following examples, in which all parts and percentages are by weight unless otherwise stated. However, the scope of the present disclosure is, of course, not limited to the formulations illustrated in these examples. Rather, examples are merely inventive to the present disclosure.

Table 1 below lists information on the raw materials used in the examples: Table 1. Raw materials used in the examples raw materials representation supplier BA Butyl acrylate Sinopharm Chemical Reagent Sty Styrene Sinopharm Chemical Reagent AA acrylic acid Sinopharm Chemical Reagent IA Iconic acid Sinopharm Chemical Reagent PRIMAL ECO-36 A commercial aqueous emulsion containing a copolymer of BA/St/AN/AA/NMA with a solids content of 47.09 wt% Dow Chemical Company APS Ammonium persulfate Sinopharm Chemical Reagent t-BHP Tertiary butyl hydroperoxide Tokyo Chemical Industry HEMA Hydroxyethyl methacrylate Tokyo Chemical Industry RHODACAL DS-4 Surfactant, sodium dodecylbenzene sulfonate Solvay Chemical ACUSOL 465 Commercial aqueous dispersion containing copolymer of AA/maleic anhydride (MA) with 40 wt% solids content Dow Chemical Company ACUSOL 505N Commercial aqueous dispersion containing copolymer of AA/MA with 35 wt% solids content Dow Chemical Company COLANYL BLUE A2R 131 Pigments Clariant LYOPRINT PT-RV thickener Huntsman DI water deionized water - Example 1 : Preparation of single-stage aqueous emulsion

In this example, a single-stage aqueous emulsion was prepared according to the following procedure: A solution containing 8.42 g of RHODACAL DS-4 and 467 g of DI water was placed in a 5-neck, 5-liter round-bottomed flask equipped with a thermocouple, condenser, and stirrer. , and heated to 84°C under nitrogen. 20.56 g IA was dissolved in 235 g DI water to form an aqueous solution, which was heated to 60°C and fed into the flask. 2.43 g RHODACAL DS-4 was dissolved in 362 g deionized water, and 27.3 g HEMA, 34.2 g AA, 1039 g BA, and 109.4 g Sty were slowly added thereto under stirring to form a first monomer emulsion. 78.7 g of the first monomer emulsion was charged into the flask, followed by the addition of a solution of 4.11 g APS in 45 g DI water. The temperature in the flask increased as the reaction progressed. When the peak temperature of 84°C was reached, the remainder of the first monomer emulsion and a solution of 1.34 g APS in 68 g DI water were gradually added over 150 minutes, during which time the flask was maintained at a temperature of 83°C to 85°C. As the addition was complete, the vessel containing the first monomer emulsion and the feed tube into the flask were rinsed with 45 g of DI water and the rinse water was added back to the flask before the flask was maintained at 84°C for an additional 15 minutes. Subsequently, 1.5 g of 0.5 wt% FeSO ₄ aqueous solution, 0.87 g t-BHP in 20 g DI water, and 0.57 g IAA in 20 g DI water were added to the flask, and the reaction was carried out for 15 minutes, after which 0.87 A solution of g t-BHP in 15 g DI water and a solution of 0.57 g IAA in 15 g DI water were fed into the flask. Then a solution of 3.62 g t-BHP in 55 g DI water and 2.3 g IAA in 55 g DI water were slowly added to the flask over 45 minutes. The flask was then cooled to ambient temperature. The pH of the resulting emulsion was adjusted to approximately 7.0 using ammonia solution, and the emulsion was further diluted to a solids content of 46 wt%. The emulsion prepared in this example was a single-stage aqueous emulsion of BA/St/AA/IA/HEMA copolymer and is referred to as Emulsion 1 in the following. Example 2 : Preparation of two-stage aqueous emulsion

In this example, a two-stage aqueous emulsion was prepared according to the following procedure: a solution containing 8.42 g RHODACAL DS-4 and 467 g DI water was placed in a 5-neck 5-liter round-bottomed flask equipped with a thermocouple, condenser, and stirrer. , and heated to 84°C under nitrogen. 20.56 g IA was dissolved in 235 g DI water to form an aqueous solution, which was heated to 60°C and fed into the flask. 2.43 g RHODACAL DS-4 was dissolved in 362 g deionized water, and 27.3 g HEMA, 34.2 g AA, 1039 g BA, and 109.4 g Sty were slowly added thereto under stirring to form a first monomer emulsion. 78.7 g of the first monomer emulsion was charged into the flask, followed by the addition of a solution of 4.11 g APS in 45 g DI water. The temperature in the flask increased as the reaction progressed. When the peak temperature of 84°C was reached, the remainder of the first monomer emulsion and a solution of 1.34 g APS in 68 g DI water were gradually added over 150 minutes, during which time the flask was maintained at a temperature of 83°C to 85°C. As the addition was complete, the vessel containing the first monomer emulsion and the feed tube into the flask were rinsed with 45 g of DI water and the rinse water was added back to the flask before the flask was maintained at 84°C for an additional 15 minutes. A second monomer emulsion was prepared in advance by dissolving 1.13 g RHODACAL DS-4 in 110 g deionized water and slowly adding 13.7 g AA and 123 g Sty thereto. The second monomer emulsion, 1.5 g of 0.5 wt% FeSO ₄ in water, 0.87 g of t-BHP in 20 g of DI water, and 0.57 g of IAA in 20 g of DI water were added to the flask and allowed to react for 15 minutes, then a solution of 0.87 g t-BHP in 15 g DI water and a solution of 0.57 g IAA in 15 g DI water were fed into the flask. Then a solution of 3.62 g t-BHP in 55 g DI water and 2.3 g IAA in 55 g DI water were slowly added to the flask over 45 minutes. When polymerization is complete, the flask is cooled to ambient temperature. The pH of the resulting emulsion was adjusted to approximately 7.0 using ammonia solution, and the emulsion was further diluted to a solids content of 46 wt%. The emulsion prepared in this example was a two-stage aqueous emulsion of a BA/St/AA/IA/HEMA//St/AA copolymer formulation and is hereafter referred to as Emulsion 2. Example 3 : Preparation of two-stage aqueous emulsion without hydroxyl-containing monomers

In this example, a two-stage aqueous emulsion was prepared according to the following procedure: a solution containing 8.42 g RHODACAL DS-4 and 467 g DI water was placed in a 5-neck 5-liter round-bottomed flask equipped with a thermocouple, condenser, and stirrer. , and heated to 84°C under nitrogen. 20.56 g IA was dissolved in 235 g DI water to form an aqueous solution, which was heated to 60°C and fed into the flask. 2.43 g RHODACAL DS-4 was dissolved in 362 g deionized water, and 34.2 g AA, 1039 g BA, and 136.7 g Sty were slowly added thereto under stirring to form a first monomer emulsion. 78.7 g of the first monomer emulsion was charged into the flask, followed by the addition of a solution of 4.11 g APS in 45 g DI water. The temperature in the flask increased as the reaction progressed. When the peak temperature of 84°C was reached, the remainder of the first monomer emulsion and a solution of 1.34 g APS in 68 g DI water were gradually added over 150 minutes, during which time the flask was maintained at a temperature of 83°C to 85°C. As the addition was complete, the vessel containing the first monomer emulsion and the feed tube into the flask were rinsed with 45 g of DI water and the rinse water was added back to the flask before the flask was maintained at 84°C for an additional 15 minutes. A second monomer emulsion was prepared in advance by dissolving 1.13 g RHODACAL DS-4 in 110 g deionized water and slowly adding 13.7 g AA and 123 g Sty thereto. The second monomer emulsion, 1.5 g of 0.5 wt% FeSO ₄ in water, 0.87 g of t-BHP in 20 g of DI water, and 0.57 g of IAA in 20 g of DI water were added to the flask and allowed to react for 15 minutes, then a solution of 0.87 g t-BHP in 15 g DI water and a solution of 0.57 g IAA in 15 g DI water were fed into the flask. Then a solution of 3.62 g t-BHP in 55 g DI water and 2.3 g IAA in 55 g DI water were slowly added to the flask over 45 minutes. When polymerization is complete, the flask is cooled to ambient temperature. The pH of the resulting emulsion was adjusted to approximately 7.0 using ammonia solution, and the emulsion was further diluted to a solids content of 46 wt%. The emulsion prepared in this example was a two-stage aqueous emulsion of a BA/St/AA/IA//St/AA copolymer formulation and is hereafter referred to as Emulsion 3. This emulsion 3 did not contain hydroxyl functionality and was used in the comparative example. Example 4-6 and Comparative Example 1-3

In Examples 4-6 and Comparative Examples 1-3, an aqueous pigment composition (in the form of a paste) was prepared by mixing all the components according to the formula listed in Table 2 for 15 minutes. Table 2: Formulas of Examples 4-6 and Comparative Examples (Co. Example) 1-3 Example 4 Example 5 Example 6 Comparative example 1 Comparative example 2 Comparative example 3 PRIMAL ECO-36 - - - 8.92 - - Lotion 1 9.11 - - - - - Lotion 2 - 9.11 9.11 - - 9.11 Lotion 3 - - - 9.23 - ACUSOL 465 0.46 0.46 - - - - ACUSOL 505N - - 0.46 - - - COLANYL BLUE A2R 131 5.25 5.25 5.25 5.25 5.25 5.25 LYOPRINT PT-RV 1.5 1.5 1.5 1.5 1.5 1.5 NH ₃ ·H ₂ O 0.35 0.35 0.35 0.35 0.35 0.35 DI water 83.33 83.33 83.33 83.98 83.67 83.79 total 100 100 100 100 100 100 representation

A 40 cm × 40 cm piece of cotton fabric was fixed on a Zimmer printing table (Mini MDF R 397 type) and covered with a screen with a 125 mesh screen line. Each paste prepared in Examples 4-6 and Comparative Examples 1-3 of the present invention is printed on cotton fabrics by screen printing. The processing parameters are rod diameter: 10 mm, pressure: 2, maximum speed, one Cycle: left-right-left. The printed cotton fabric was dried and cured at 150°C for 3 minutes.

Each coated cotton fabric was characterized by the following technique. Colorfastness to Crocking

The rub color fastness of each coated fabric was characterized according to AATCC 8-2005, and the dyeing Gray Scale was measured on a colorimeter according to AATCC Evaluation Procedure 2 (2005). The characterization results are summarized in Table 3, where smaller gray scales and larger ΔE* values indicate darker and undesirable staining colors. Table 3: Colorfastness to Wet Crocking (Colorfastness to Wet Crocking) wet friction Grayscale-Staining ΔE* Example 4 2.5 21.23 Example 5 2.5 20.48 Example 6 2.5 20.04 Comparative example 1 2 23.08 Comparative example 2 2 22.95 Comparative example 3 2 27.05 Washing resistance

The laundering resistance of each coated fabric was characterized according to AATCC 61-2003, and the gray scale of the color change was measured on a colorimeter according to AATCC Evaluation Procedure 1 (2002).

Washing conditions:

Cycle 1: 40℃, water and commercial washing liquid (20 ml), wringer 1000 rpm, 1 hour washing + 2 hours drying at 66℃;

Cycle 2: 60℃, water and commercial washing liquid (20 ml), winch 1000 rpm, 1 hour washing + 2 hours drying at 66℃;

Cycle 3: 90°C, water and commercial washing liquid (20 ml), winch 1000 rpm, 1 hour washing + 2 hours drying at 66°C.

The characterization results are summarized in Table 4, where smaller grayscale changes and larger ΔE* values indicate more significant and undesirable color changes. Table 4: Washing resistance Gray scale change at 40℃ ΔE* at 40℃ Gray scale change at 60℃ ΔE* at 60℃ Gray scale change at 90℃ ΔE* at 90℃ Example 3 4.5 1.01 4 1.93 3.5 3.1 Example 4 4.5 0.46 4.5 1.4 3.5 2.38 Example 5 4.5 0.94 4 1.98 3.5 3.16 Comparative example 1 4.5 0.86 4 2.01 3 3.35 Comparative example 2 4.5 1.03 4 2.26 3 3.7 Comparative example 3 4 1.46 4 2.24 3 3.66

As can be seen from the characterization results listed in Table 3 and Table 4, the past results of Examples 4 to 6 were comparable to those of the Comparative Examples in both the rubbing color fastness and the washing resistance. Sexual achievement improved significantly.

In addition, it was further found that by using the process of Examples 5 and 6 prepared using two-stage emulsions, further improvements were achieved relative to Example 4 including a single-stage emulsion.

without

Figure 1 is a schematic diagram of a coated article according to an embodiment of the present disclosure; and

Figure 2 is a cross-section of the coated article shown in Figure 1.

Claims (10)

A formaldehyde-free aqueous pigment composition comprising: (A) an aqueous emulsion comprising a hydroxyl-functional copolymer derived from the polymerization of monomers comprising from 0.2 wt% to 15 wt% of at least one ethylenically unsaturated C ₂ -C ₁₂ carboxylic acid monomer containing hydroxyl groups, 70 wt% to 95 wt% of at least one ethylenically unsaturated C ₂ -C ₁₂ monocarboxylic acid monomer, 0.2 wt % to 15 wt% of at least ethylenically unsaturated C ₂ -C ₁₂ dicarboxylic acid monomers; (B) an aqueous dispersion comprising at least one ethylenically unsaturated C ₂ -C ₁₂ carboxylic acid monomer derived from Carboxylic acid group functionalized (co)polymers of polymerized monomers; (C) Pigments; and (D) Thickeners. For example, the formaldehyde-free aqueous pigment composition of claim 1, wherein the aqueous emulsion has the following two-stage emulsion: (i) a first stage component comprising the hydroxyl functional copolymer; and (ii) a second stage component comprising a (co)polymer derived from the polymerization of monomer(s) including one or more ethylenically unsaturated monomers; The weight ratio between the first stage component and the second stage component is 20:1 to 1:1. The formaldehyde-free water-based pigment composition of claim 2, wherein the hydroxyl-containing ethylenically unsaturated C ₂ -C ₁₂ carboxylic acid monosystem is selected from the group consisting of: (meth)acrylic acid hydroxyl (C ₁ -C ₁₂ ) Alkyl ester, crotonic acid hydroxyl (C ₁ -C ₁₂ ) alkyl ester, pentenoic acid hydroxyl (C ₁ -C ₁₂ ) alkyl ester, 3,3-dimethylpentenoic acid hydroxyl (C ₁ -C ₁₂ ) Alkyl ester, hexenoic acid hydroxyl (C ₁ -C ₁₂ ) alkyl ester, heptenoic acid hydroxyl (C ₁ -C ₁₂ ) alkyl ester, octenoic acid hydroxyl (C ₁ -C ₁₂ ) alkyl ester, nonenoic acid hydroxyl ( C ₁ -C ₁₂ ) alkyl ester, decenoic acid hydroxy (C ₁ -C ₁₂ ) alkyl ester, fumaric acid hydroxy (C ₁ -C ₁₂ ) alkyl ester, di(hydroxy (C ₁ -C ₁₂ ) alkane (Hydroxy (C ₁ -C 12 ) alkyl) ((C 1 -C ₁₂ ) alkyl) fumarate, (Hydroxy (C ₁ -C ₁₂ ) alkyl) fumarate, (Hydroxy (C 1 -C ₁₂ ) alkyl) fumarate ₁₂ ) Alkyl ester, bis(hydroxy(C ₁ -C ₁₂ )alkyl) maleate, (hydroxy(C ₁ -C ₁₂ )alkyl)((C ₁ -C ₁₂ )alkyl) maleate Enedioate, 2-methylmaleic acid hydroxy (C ₁ -C ₁₂ ) alkyl ester, di(hydroxy (C ₁ -C ₁₂ ) alkyl) 2-methyl maleate, ( Hydroxy (C ₁ -C ₁₂ ) alkyl) ((C ₁ -C ₁₂ ) alkyl) 2-methyl maleate, itaconic acid hydroxy (C ₁ -C ₁₂ ) alkyl, di(hydroxy (C ₁ -C ₁₂ )alkyl) itonate, (hydroxy(C ₁ -C ₁₂ )alkyl) ((C ₁ -C ₁₂ )alkyl) itonate, 2-methyl-iconate Acid hydroxy (C ₁ -C ₁₂ ) alkyl ester, di(hydroxy (C ₁ -C ₁₂ ) alkyl) 2-methyl-iconate, (hydroxy (C ₁ -C ₁₂ ) alkyl) ((C ₁ -C ₁₂ )alkyl) 2-methyl-iconate, hydroxy(C ₁ -C ₁₂ )alkyl glutenedioate, bis(hydroxy(C ₁ -C ₁₂ )alkyl)glutenedic acid Ester, (hydroxy (C ₁ -C ₁₂ ) alkyl) ((C ₁ -C ₁₂ ) alkyl) glutenedioate, muconic acid hydroxy (C ₁ -C ₁₂ ) alkyl ester, bis (hydroxy (C ₁ -C ₁₂ )alkyl) muconate, (hydroxy (C ₁ -C ₁₂ ) alkyl) ((C ₁ -C ₁₂ ) alkyl) muconate, and combinations thereof; the ethylenically unsaturated The C ₂ -C ₁₂ monocarboxylic acid monosystem is selected from the group consisting of: (meth)acrylic acid, crotonic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decene Acid (caproleic acid), its salt, anhydride, or (C ₁ -C ₁₂ ) alkyl ester; the ethylenically unsaturated C ₂ -C ₁₂ dicarboxylic acid monosystem is selected from the group consisting of: trans-butyl Enedioic acid, maleic acid, 2-methylmaleic acid, itaconic acid, 2-methyliconic acid, glutenedic acid, muconic acid, and their salts, anhydrides, or esters; The ethylenically unsaturated C ₂ -C ₁₂ carboxylic acid monosystem of the aqueous dispersion (B) is selected from the group consisting of: (meth)acrylic acid, crotonic acid, pentenoic acid, hexenoic acid, heptene Acid, octenoic acid, nonenoic acid, decenoic acid, fumaric acid, maleic acid, 2-methylmaleic acid, itaconic acid, 2-methyliconic acid, pentene Diacid, muconic acid, and salts, anhydrides, or (C ₁ -C ₁₂ ) alkyl esters; and the ethylenically unsaturated monosystem of the second stage component is selected from the group consisting of: ( Methacrylic acid, crotonic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, fumaric acid, maleic acid, 2-methylmaleic acid Enedioic acid, itaconic acid, and their salts, anhydrides, (C ₁ -C ₁₂ ) alkyl esters, or hydroxy (C ₁ -C ₁₂ ) alkyl esters; hydroxyl functional ethylenically unsaturated C ₂ -C ₁₆ Carboxylic acid; styrenic monomer; (meth)acrylamide; diene; (C ₁ -C ₁₀ ) vinyl carboxylate; (meth)acrylonitrile; and combinations thereof. For example, the formaldehyde-free water-based pigment composition of claim 2, wherein the hydroxyl-containing ethylenically unsaturated C ₂ -C ₁₂ carboxylic acid monosystem is selected from the group consisting of: hydroxymethyl methacrylate, hydroxymethyl acrylate , hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate, hydroxybutyl acrylate, hydroxyethyl crotonate, and combinations thereof; the olefin series The unsaturated C ₂ -C ₁₂ monocarboxylic acid monosystem is selected from the group consisting of: acrylic acid, methacrylic acid, crotonic acid, acrylic acid (C ₁ -C ₆ ) alkyl ester, methacrylic acid (C ₁ -C ₆ ) alkyl ester, crotonic acid (C ₁ -C ₆ ) alkyl ester, and combinations thereof; The ethylenically unsaturated C ₂ -C ₁₂ dicarboxylic acid monosystem is selected from the group consisting of: fumaric acid, Maleic acid, itaconic acid, (C ₁ -C ₆ ) alkyl fumarate, di((C ₁ -C ₆ ) alkyl) fumarate, maleic acid ( C ₁ -C ₆ )alkyl ester, di((C ₁ -C ₆ )alkyl) maleate, itaconic acid (C ₁ -C ₆ )alkyl ester, itaconic acid di((C ₁ -) C ₆ )alkyl ester), and combinations thereof; The ethylenically unsaturated C ₂ -C ₁₂ carboxylic acid monosystem of the aqueous dispersion (B) is selected from the group consisting of: methacrylic acid, acrylic acid, crotonic acid , fumaric acid, maleic acid, itaconic acid, methacrylic acid (C ₁ -C ₆ ) alkyl ester, acrylic acid (C ₁ -C ₆ ) alkyl ester, crotonic acid (C ₁ -C ₆ ) Alkyl ester, (C ₁ -C ₆ ) alkyl fumarate, di((C ₁ -C ₆ ) alkyl) fumarate, (C ₁ -C ₆ ) alkyl maleate Ester, di((C ₁ -C ₆ ) alkyl) maleate, (C ₁ -C ₆ ) alkyl itonate, di((C ₁ -C ₆ ) alkyl) itonate , and combinations thereof; and the ethylenically unsaturated monosystem of the second stage component is selected from the group consisting of: methacrylic acid, acrylic acid, crotonic acid, fumaric acid, maleic acid, Iconic acid, methacrylic acid (C ₁ -C ₆ ) alkyl ester, methacrylic acid hydroxyl (C ₁ -C ₆ ) alkyl ester, acrylic acid (C ₁ -C ₆ ) alkyl ester, acrylic acid hydroxyl (C ₁ -C ₆ ) alkyl ester, crotonic acid (C ₁ -C ₆ ) alkyl ester, crotonic acid hydroxy (C ₁ -C ₆ ) alkyl ester, fumaric acid (C ₁ -C ₆ ) alkyl ester, di((C ₁ -) C ₆ )alkyl) fumarate, hydroxy (C ₁ -C ₆ ) fumarate, di(hydroxy (C ₁ -C ₆ ) alkyl) fumarate, ( Hydroxy (C ₁ -C ₆ ) alkyl) ((C ₁ -C ₆ ) alkyl) fumarate, maleic acid (C ₁ -C ₆ ) alkyl ester, maleic acid hydroxyl (C ₁ -C ₆ )alkyl ester, di((C ₁ -C ₆ )alkyl) maleate, di(hydroxy(C ₁ -C ₆ )alkyl)maleate, ( Hydroxy (C ₁ -C ₆ ) alkyl) ((C ₁ -C ₆ ) alkyl) maleate, itaconic acid (C ₁ -C ₆ ) alkyl ester, itaconic acid hydroxy (C ₁ - C ₆ ) alkyl ester, di((C ₁ -C ₆ )alkyl) itonate, di(hydroxy(C ₁ -C ₆ )alkyl) itonate, (hydroxy(C ₁ -C ₆ ) Alkyl) ((C ₁ -C ₆ )alkyl) itaconate, styrene, (meth)acrylamide, butadiene, isoprene, vinyl acetate, (meth)acrylonitrile, and combinations thereof. For example, the formaldehyde-free water-based pigment composition of claim 1, wherein the composition has a solid content of 2 wt% to 20 wt% based on the total weight of the composition; The aqueous emulsion (A) has a solid content of 30 wt% to 60 wt% based on the total weight of the aqueous emulsion; The aqueous dispersion (B) has a solids content of 25 wt% to 55 wt% based on the total weight of the aqueous dispersion; and Based on the total weight of the composition, the composition includes 2 wt% to 18 wt% of the aqueous emulsion (A), 0.05 wt% to 5 wt% of the aqueous dispersion (B), 0.5 wt% to 10 wt % of the pigment, 0.1 to 15 wt% of the thickener, and the balance water. The formaldehyde-free water-based pigment composition of claim 2, wherein based on the total solid weight of the first-stage component and the second-stage component, the first-stage component further includes 1 wt% to 16 wt% of at least An additional comonomer (comomoner) selected from the group consisting of: styrenic monomers, (meth)acrylamide, butadiene, isoprene, vinyl acetate, ( Meth)acrylonitrile, and combinations thereof. For example, the formaldehyde-free water-based pigment composition of claim 1, wherein the composition contains 0.5 wt% to 10 wt% of the pigment based on the total weight of the composition, and the pigment is selected from the group consisting of: Even Nitrogen pigments, phthalocyanine pigments, allionquinone pigments, indigo pigments, quinacridone pigments, dioxins Pigments, arylmethane pigments, and compositions thereof. For example, the formaldehyde-free water-based pigment composition of claim 1, wherein the composition contains 0.1 wt% to 15 wt% of the thickener based on the total weight of the composition, and The thickener is selected from the group consisting of: polyacrylic acid thickener, polyurethane thickener, cellulose thickener, polyether thickener, polyester thickener, aliphatic acid thickener Thickeners, aliphatic alcohol thickeners, inorganic salt thickeners, alkanolamide thickeners, amine oxide thickeners, natural gum thickeners, and combinations thereof. A coated article comprising a substrate and a coating at least partially covering one or both sides of the substrate, wherein The coating is formed from the formaldehyde-free water-based pigment composition according to any one of claims 1 to 8. For example, the coated article of claim 9, wherein the substrate is selected from the group consisting of: woven fabric, non-woven fabric, paper, cardboard, wood, wool, cotton, rayon, silk, leather, Rubber, plastic film/sheet, metal film/sheet, fiberglass fabric, carbon fiber fabric, cement, concrete, and combinations thereof.

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